Method of desulfurizing hydrocarbon oil using hydrogen and a cobalt ferrite or nickel ferrite catalyst



Sept. 3, 1957 METHOD OF DESULFURIZING HYDROCARBON OIL USING HYDROGEN AND A COBALT FERRITE OR NICKEL FERRITE. 'CATALYST Filed April 30, 1956 f P. N. RYLANDER ET ALI Pau/MRy/ander W/lfardJZ/mmersc/ried United States Patent C 4MET-HOD -O-F lDESULFURIZING JHYDROCARBON `VtQIL .USING HYDROGEN AND .ALCOBALT I,FER- OR vlICKEL =CAI`ALXST Application April 30, 195,6, VSerialllo. 531,498 -8 Claims. ,(Cl. 196-28) This invention relates to the tdesulfurizing of hydrocarbon oils and in particular it concerns the use of novel catalysts for the hydrodesulfurization of hydrocarbon oils containing organic sulfur compounds. This application is acontinuation-in-part of our vSerial No. 535,269, led YSeptember 19, 1955 andnow abandoned.

'Betroleum or other hydrocarbon oils which Vcontain appreciable amounts of sulfur .compounds .are objectionable ,for use as fuel, lubricating oils, solvents, or cracking stocks and the like. Frequently virgin and Cracked naphthas must be desulfurized before blending into ,gasoline or .before further processing, .such as hydroforming, to improve their .oo tane number- Thehigh .sulfnroomponents, es. eolie still naphtha, of gasoline require -desnlfnrization in order `to prosineea blended gasoline rneeting the reanir.enient oftlovvsnlfur oo ntent .A nnrnher of catalysts are available for the hydrodesulfurization Aof .virgin naphthas, but if they are .employed in ,hydroriesnl- ,foiiing olelinio naphthas snoh .as .thermallyor oatalytieal- '1y ersehen naphthas, they catalyze indiscriminate desniiorizotion and hydrosenation of the higher oetane oletins ,to -nrotlnoe lower oetane paratiinsyThe ,oletlnie krntphthas, e a ooke still naphtha, niay .sniiera loss o f .l0 to 2.0 octane nninhersi ,In addition, a Considerable amount .of expensive hydrogen ,is used in satnring theoletins.

.en .obi-eet .of this invention is to Provide .a methodanti means for desulfurizing hydrocarbon oils which utilizes highly active and etfecti-ve hydrodesulfuriration catalysts. another object is to prov id e.-selectiv desulfurization cat.- alysts nsefnl for oesnlforizing olefinie hytlroearhon oils with a niininlorn oonsnnintion of hydrogen A n impor.- tant ohieot of this invention is to .Provide .an eeonornioal method and means for achieving a high degree of desnifurization of olenic naphthas while maintaining satura- A*tion,'i. e. hydrogenation, of the olenic components at a and thereby obtaining a desuliurizel oleni nanhtha Whose notano number has Anot .been snhstantially reduced during hydrodesulfurization. Other objects will heeorne apparent from the detailed Ydeserintion of our invention.

lilies been discovered .that oohaltons ferrite and .nickelons territo; .which are ehernieal compounds having a .sninel strnetnre and Corresponding with the formulae CoTresQi and NiFeaOi respectively, .are highly eiteotive lanalysts ,for the hyorodesnl-,fnrization of hydrocarbon o ls.-A They niay he .ernnloyed alone or as the essential components of a contact or catalyst mass. Desulrfurization 4of the hydrocarbon 4oil may be carried out by con- Vtacting the yoil at a .temperature between about 600 and .1099 F- :inthe nresenee of hydrogen, usually onder a h'ydrogen'partial pressure of between 100 and 3,000 p. s. i.V g. `(but .preferably less than V1500 p. s. i. g. H2 if an foleiinio naphtha is used) .with the oohaltons ferrite or nickelous ferrite catalyst. A high degree of desuliiuization of the olenic naphtha is obtained along with amuch lesser degree of hydrogenation of the oleflnic .SQllstiIlllellts ofthe ,naphtha 'ifobaltons yferrite .and niolselons ferrite .are not rnere soars? Patented Sept;V 3, 17957 Aphysical mixtures .of their .metal oxidecomponents..(.co ibalt oxide plus ferric oxide and ynickel .oxide plus fier-ric oxide, respectively). They .are true chemical. compounds whichhave Va spineltype structure. In the rSpinel structure the oxygen `atoms are .arrangedon.altace-centered .cubic lattice, in cubic closepackng, the coba-ltfor nickel atoms beinge surrounded .by tetrahedral .groups..offf0.ur .oxygen atoms `and .the ferric atoms by octahedral groups Yof six atoms. These metal .,ferrites ampara-magnetic. `Cobaltous Iferrite has vacubic structure which `measures 8.36" A along the side and has .a molecular .volume .of 5B4 1O24 cc. VIt is gbrown in .colorand has a .specic gravity of 5.19. Niekelous ferr-ite measures 1.8.43- A .along the `side .and hasa molecular volume .of 580139)( ,l0-24 cc. AItisbrown in .colorand hasa `specic gravity .of 5.2.6.8. Y

The metal ferrite lmay be prepared by commingling -a ,Cobalt and/ or nickel ,compound rwhich :affords thebxide of cobalt and/ or nickel with an iron compound which affords an .oxideof ironand then calcining .theintimate mixture by heating it at a temperature between .about 0va nd 20 0,0,F. for aperiod ofabout 1 10,24zfhours. KACobalt compounds which may be used `.are inorganic .c obalt comppllnds such as1CoCO3, 2CoCO3.3,Co(OH 2:1-120, Qo,(O,H),2, V.Co2O3.3HzO, COQ, YCosOfi,(309.015,

Co (NO3)2.6H2O

as Well as organic cobalt compounds such asQoQ2.@,4and V.thelilre rWhen preparing the knlokelons ferrite catalyst, .eornponnds vvhieh ,afford niokel orsirle at `the elevated alcination temperature, and which are .theretore useful .in preparing the nickelous ferrite catalyst, are those such as NiO; NiaQs; NisOa; ,NiaO4,.2H.2O;LlNi (-Oli)a;

Ni(oH)2.i/2-H2o; Nioo; zNicosNioHazAHzo; Y nicnenzo; Nnnozlazrno (niekel formate);

fNiV(C2H3O 2)2 (nickel acetate). The .iron compounds .employed in forming .the cobaltous or nickelous ferrite are usually inorganic ferric and ferrous compoundssuch ,as Fe(OH)3, Fe(OH)2, FezOs, FeG,A iFeaOti, 'FeFz, FeClz, FeCla, Fe(NO3I)3.i6 -01 l9H2O, FC(NO3)2, 6H20, as Well as organic iron compounds such as Fe C3H5O3 2.3H2O ...t-ferrous laotate), .F.eatCzOils (ferrie oXa'late),

Fe CHOz 3 U(.ferric qformate) `and `the like. When preparing the Aco.- .baltous ferrie catalyst `a mixture o f fCoNOgHGlilaOg and FeNOaBHfzO may conveniently be .employed ,because asV the two materials are heated a liquid is formed .which mixes thoroughly as Water is boiled oil and the .temperyature raisedto the level necessary V,to/form ,the eohaltpus -ferrite. A mixture .of nickel oxide and ferr-ic oxide are highlysuitable for use yin preparing the nickelous ferrite catalyst. Y Y

The cobalt and/or nickel compounds Vand the iron ACompound yare intimately mixed `in the desired propor.- tionsV before being calcined. The kintimate mix-ture of vthe cobalt and/or nickel onipoundrwith the, non cpm.- pound should contain ,the ,cobalt and/or ni el` aud-the iron a molar ratio of approximately/40,2 to y2,*0-morls lot' cobalt and/ or nickelper-mol of iron. Since'themolar ratio of cobalt to ironlandthe molarratioof ',nieke'l .to iron ,in the cobaltous ferrite .and nickelouslferrit'es respectively, is 1:2, the use of an ,excess of ,either the iron or the cobalt and/ or nickel in the mixture which isheated vserves ,no especially useful functionbut serves' merely as an Vexte'rlilerV for the eobaltons ferriteor the niokeloiis ferrite. Thus it is preferred to c aleine--a mixture vwhich eontains aoobalt kto iron molar ratio .'.oilrZflor .a niels?! to iron zinolar ratio of 15.2...

The cobalt and/or nickel compound is intimately mixed with the iron compound before calcination. This may be done by ball milling the particular cobalt and/or nickel compound with the iron compound in the dry or Wet state, preferably the latter. For example, la water or methanol slurry of the mixture may be ball milled until finely ground and mixed. lf the cobalt and/or nickel together with the iron compounds are completely soluble in a minor amount of water, vigorous mixing is not necessary. After an intimate mixture is obtained, the water, methanol, or whatever slurrying medium is used, is vaporized in a separate step or during the early stages of the calcination. While this intimate mixture may be calcined at a temperature between about 1400 and 2000 F. or higher, a temperature of at least about 1800 F. is preferred. It is essential to carry out the calcination at a temperature of at least 1400 F. in order to obtain an active catalyst; for if the calcination is carried out at a much lower temperature e. g. 1200 F. or less, or if 4the mixture of the cobalt and/ or nickel compound with rcarried out over a course of 1 to 24 hours or more, suitably 3 to 18 hours. Because the catalytic material is -produced at such an elevated temperature and is stable at such temperatures, it has an inherent advantage over other desulfurization catalysts wherein the temperature of regeneration of the catalyst must be carefully controlled to about 1200 F. or lower to avoid sintering and deactivation.

The calcination product may be used in a desulfurization process in the form of fragments as obtained from the calcination step, or it may be pulverized and pelleted with the aid of l-2% of Sterotex (hydrogenated corn oil), stearic acid, or the like which are employed as binders and subsequently burned from the pellets. if the catalyst is employed in pelleted form, it can be pelleted together with a carrier such as activated alumina, bauxite, or the like. The various carriers or spacing agents, upon which the calcination product may be extended, can be Vincorporated in the finished catalyst by pulverizing the carrier material e. g. activated alumina, hydrous alumina gel, commingling it with the pulverized calcination product, then pelleting it with the aid of a binder, and finally burning the binder therefrom with dilute oxygen at a temperature of about 500 to 1000 l5".` (but not higher than 1200 F.). While the cobaltous ferrite or the nickelous ferrite may be extended upon a carrier material to reduced the cost, it is preferred to use an unsupported Vmetal ferrite catalyst when desulfurizing an olefnic naphtha because the unsupported catalyst generally displays aV greater preference for desulfurization rather than parafnation of the olefins (which are generally of higher octane number than the corresponding paraiiins).

Hydrocarbon oils which may be desulfurized are those such as petroleum and fractions thereof, coal hydrogenation oils, shale oil, and the like which contain objectionable amounts of sulfur compounds, nitrogen compounds and oxygen compounds. The oil may be a virgin or Vcracked distillate. Virgin or cracked naphthas are particularly suitable feeds to the process of this invention,

although higher boiling oils e. g. kerosene, gas oil, etc. may be employed. Olelinic naphthas such as contain an olefin to paraffin ratio in the range of 3:1 to 1:3 are particularly suitable feed stocks because minimum saturation of the olefin content occurs during the hydrodesulfurization process. An outstanding example of a high sulfur olefinic naphtha is a naphtha produced by the'coking of a high sulfur reduced crude by conventional methods such as delayed coking or fiuidized coking methods. Such a naphtha is exceedingly more difficult to desulfurize by conventional methods than are the olefinic naphthas produced by'thermal cracking or by Vcatalytic cracking.

The hydrocarbon oil is desulfurized by passing it together with hydrogen through the reactor containing the catalyst. The catalyst may be contained in the reactor in tubes, trays, or other appropriate containers, or it may be employed in the fiuidized state. The conditions employed in desulfurization when using our catalyst will of course vary to some extent dependent upon the type of hydrocarbon oil to be desulfurized and the extent of desulfurization desired. A temperature of 600 to 1000 F. may be used, the higher temperatures being employed in desulfurizing higher boiling feed stocks. When desulfurizing naphtha fractions atemperature of about 600 to 800 F., preferably about 750 F., may be employed. Under such conditions the naphtha is desulfurized while in the vapor state, whereas when desulfurizing algas oil, a liquid phase is present. A pressure ranging from about or 3000 p. s. i. g. or higher may be employed in the reactor. The oil is contacted with the catalyst in the presence of hydrogen which may be employed in the amount of 500 to 5000, preferably 1500 to. 3000 s. c. f./ bbl. oil. The hydrogen may consist of introduced outside hydrogen as is employed in a conventional hydrofining type operation, or it may be generated within the reactor by dehydrogenation of the naphthenes present in the feet stock as occurs infautofining. Space velocities of between 0.5 to as high as 20 volumes of oil per hour per volume of catalyst, preferably between 2 to 10 volumes of oil'per hour per volume of catalyst, may be employed. v

The higher space velocities are used with the more easily desulfurized stocks such as virgin naphtha, whereas the lower space velocities of about 2 to 5 are employed with the more diicultly desulfurized stocks such as coke `still naphtha, higher boiling stocks such as gas oils, and

the like.

After the catalyst has been used for a sufficient length of time so that its activity begins to decline, it may be regenerated by burning the hydrocarbonaceous material therefrom employing diluted oxygen such as a mixture of flue gas with air. Because of the thermal stability of the catalyst, the temperature of regeneration need not be kept below 1200 F. as is necessary to avoid deactivation of presently available commercial hydrodesulfurization catalysts. The temperature may be as high as about l600l800 F. Regeneration at these higher temperatures is more rapid and the down-time of the hydrodesulfurization unit can be decreased. Not only will the use of our catalyst minimize costly equipment necessary to control regeneration of the catalyst, but it will have the added economic incentive of reducing unit downtime.

The effectiveness of the nickelous ferrite as a catalyst for hydrodesulfurizing hydrocarbon oils was demonstrated in a number of experiments. These experiments show the extreme importance of carrying out the calcination of the nickel compound and the iron compound at a temperature of 1400 F. or higher in order to obtain nickelous ferrite which is highly active as a desulfurization catalyst. Five different catalytic materials were prepared and their effectiveness evaluated for desulfurizing a coke still naphtha. The catalysts used in runs 1 through 3 inclusive were prepared by calcining (using different calcination temperatures in preparing each catalyst) an intimate mixture of one mol of NiO and one mol of FezOa (the mixture thus having a molar ratio of nickel to iron of 0.5 :1). The catalyst used in runs 4 and 5 was prepared from an intimate mixture of NiCO3 and F6203. The catalyst used in run 4 was prepared by calcining a mixture containing one mol of NiCO3 and one mol of FezOa (0.5 mol ofnickel per mol of iron), and the catalyst used in run 5 was prepared from a mixture Vcontaining'Zmols of NiCO3` and 1 mol of Fez03 (1.0 mol of nickelper mol of iron). The technique employed in preparing the catalysts was to ball mill a mixture of the nickel` compound and the iron compoundwith methanol, dry the resultant slurry, and then calcine it for about 18 to 24 houfs at lthe dene'd vcalcina'tiun at'emperatur. The frag ments -rproduced upon calcination 'of ithe .mixtures was grfound and then 'employed `in the .hydrod'esulfurization runs. y

In carrying Yout the hydrodesulfurization runs, samples of the catalyst compositions 'to 'be tested were placed in the center section of an electrically heated n'ei'ch (id.) :stainless ."steel vertical reactor approximately `38 i'nch's 'lng The section 'above the .catalyst was packed with glass beads to `act as a preheat l'section if0r`the1incoming feed. 4Samples. `of ckestill naphth'a .(.which were obtained `from the delayed coking of a1mixt'ure :of high sulfur 'reduced crudes L-primarily :of `Wst YTeexa's Jorigin) 'having sulfur contents ranging between-0:55aa'nd 0i6'5 `and bromine numbers of approximately 70 .were passed to- 1 gethe'r `with once-through hydrogen (ata rate approximating 2000 standard cubic feetof hydrogen :per bbl. of naphtha') through the top of the downow reactor. 'All of the runs were carried out at fa temperature of about 750 F., .a-liqu'id hourly 'spacevelocity ofaabout r2.0,.and a partial pressure of hydrogen of about .1` 000;p.1s. fi. 5g. ."lhe eliuent -was collected in ia Apressurizedreceiver and the naphtha 1 condensed therein. Periodically, .the :liquid contents of `the pressurizedrec'eiver were removed (after samples `of 100 .to 250 cc. had accumulated) and the sulfur lContent of the desulfurized naphtha samples was determined. This provided a lcontinuous lindication of the desulfurization ability -of the catalyst as the run progressed and thus indicated catalyst life. The effectiveness of the Various catalytic masses prepared 'by calcination at `various ltemperatures are shownin Table Iiwhich follows:

lCatalyst ratio of 1:1. I

The percentage desulfurization of the oil which was obtained with the various catalysts tested is graphically shown in the ligure. ln this ligure the extent of desulfurization is plotted versus the volumes of oil per volume of catalyst. The runs 1, 2, 3, and 4 correspond with catalysts A, B, C, and D, respectively. It is apparent from the graphical presentation in the iigure that the intimate mixture of the nickel and iron compounds must be calcined at a temperature of at least l400 F. to obtain a highly active desulfurization catalyst. X-ray analyses of the catalyst used in runs l-5 substantiate that a calcination temperature of at least l400 F. is necessary in order to produce a substantial amount of nickelous ferrite. Run 5 indicates that a highly active nickelous ferrite desulfurization catalyst can be prepared from an intimate mixture of the nickel and iron compounds containing a molar ratio of nickel to iron of 1:1.

A comparison of the nickelous ferrite catalyst with a commercial CoOs-MoOa-AlzOa catalyst was made.

prepared by calclnng mixture containing Nl:Fe molar 'Ehe @commercial icatalyst, `which contained 3% :C00 :and 9%A .Mo 3, :was `u'se'd to fhydrodesulfurize'a coke naphtha. having a sulfur content of 0.55% anda bromi-ne number lof 70 employing the same hydrodesulfurization conditions ras used in runs `l-5 -i. e. ajternperature :of 750 F., a space velocity of 2.0, a partial pressure -iof hydrogen of 1000 p. s. i; g. at a rate of 2000 s. c. f. Hz/bbl. of naphtha. Samples of the desulfurized oil were yperiodically collected and analyzed for sulfur content and bromine number. The percentage vof -reduction in the bromin'e number -is hereinafter termed percentage vfdicitrl f the selectivity 'O'f th catalyst and desulfrization in Apreference to'hydrogena- (tion of the oletins .is obtained Vby vdividing the Y percent desulfurization by vthe .percent paraftination; when the selectivity is 1.0, the catalyst-displays no selectivity whatsoever. vIn Table Il which follows', a comparison iljetween the `nickelous 4ferrite vcatalyst vof run y1 fand [th commercial catalyst is made. Y

1' Selectlvity`=Percent VDesulfurlzation Percent Paralnation.

2 Cobalt oxide-#molybdenum oxide-alumlua.

:It isapparentfrom theabove data thatfnickelous ferrite is anextremely active desulfurization catalyst. The extento'f its superiority would be `even more pronounced if fthe desulfurization runs jhad .been `carried -out at less .severe :conditions wherein a lesser extent ofdesulfuriza- .tion would-be obtained. VIt lwill further be noted thatthe nickelous ferrite catalyst ris 50% more selective for desulfurization in preference 'to .paraflinatiom and .therefore .thexdesulfurized gasoline would retaina .largerainount .of the .higher octane number olens.

i'vlhefeiectiveness .ofcobaltous ferrite in thehydrodesulfurization of hydrocarbon oils wasdemonstrated .in a number vof experiments. These experiments show the :extreme importance of using the chemicalcompound cobaltous ferrite rather than a mere physical mixture of cobalt andiron oxide. Threedifferent catalytic materials were yprepared and their effectiveness evaluated fordesulfurization andfhydrogenation of the olefns present .in l-the olenicnaphtha. Catalyst E. was prepared b5/heating `an iintimate mixture @of :Co(NO3)12-'.6H2O and -FetNOa )s 9H2`O the mixture having a molar ratio of cobalt to iron of 1:2, to a temperature of 1400" F. and maintaining it at that temperature overnight (about 18 hours). The product was identilied by X-ray diffraction analysis as consisting of cobaltous ferrite with some ferric oxide. Catalyst G was made in the same manner as catalyst E except that the intimate mixture of cobalt nitrate and ferrie nitrate was heated to only 750 F. X-ray diffraction analysis of catalyst G revealed that it contained no cobaltous ferrite. Catalyst F Was made in the same manner as catalyst E except that CoCO3 and FezOs were used in place of the nitrates of cobalt and iron. X-ray analysis of catalyst G showed that cobaltous ferrite hady been formed.

The catalysts evaluated were prepared by pulverizing the fragments obtained from the heating steps in the preparation of catalysts E, F, and G, and then pelleting the Vpowder to form 1A inch pellets using about 2% Sterotex.k The Sterotex was burned from the pellets at about 850 with air. Catalyst compositions E, F, and G were then evaluated individually. Samples of these cat-V 7 Valyst compositions were used to desulfuriae a coke still naphtha having a sulfur content of 0.95% and a bromine number of 75 in the apparatus and under the operating conditions previouslyr described. The results obtained with these catalyst compositions are shown in ITable Ill which follows:

Table III Percent. Percent Selec- Run No. Catalyst Desuliuri- Parantivity 3 zatlon ation 1 Catalyst had cobaltous ferrite as active component.

2 Catalyst composition had no cobaltous ferrite, only CoaOH-FegO; as a physical mixture. i `Seiectivity= percent desulfurlzationpercent paramnation. The above table shows the excellent ability of cobaltous ferrite for catalyzing the hydrodesulfurization of a hydrocarbon oil. Comparison of the desulfurization results obtained in runs 7 and 8 with run 9 shows the extreme importance of using the chemical compound cobaltous ferrite rather than a physical mixture of cobalt oxide .and iron oxide for desulfurizing the oil. A comparison of these same runs further illustrates that low temperatures such as 750 F. cannot be used in preparing cobaltous ferrite and likewise will not produce a composition which is effective as a desulfurization catalyst. The percentage of paraination of the coke still naphtha should also be noted. When using the cobaltous ferrite catalyst of runs 7 and 8 a selectivity of approximately 2 or higher was obtained, but when using the physical mixture of cobalt oxide and iron oxide as the catalyst the selectivity was only about 1.1. It is important to note,

y however, that with the cobaltous ferrite catalyst a very high degree of desulfurization can be obtained while minimizing the degree of paralination of the olens. This peculiar ability of the cobaltous ferrite catalyst enables a petroleum rener to desulfurize an olefnicV naphtha fraction while minimizing the paraination of oleiins and thus minimizing the loss in octane number of the desulfurized naphtha. The economic advantage of using such a catalyst is obvious.

Thus having described our invention what is claimed is:

l. The method of desulfurizing a hydrocarbon oil containing organic sulfur compounds which comprises contacting said oil in the presence of hydrogen at a temperature between about 600 and 1000 F. with a catalyst containing as the essential component at least one metal ferrite selected from the group consisting of cobaltous ferrite and nickelous ferrite which metal ferrite is prepared by calcining an intimate mixture of a com- .Y 8 pound affording an oxide of iron and a compound afford; ing an oxide of a metal selected'from the class consisting of cobalt and nickel, the intimate mixture containing the metals in the following radio:

Molar ratio of cobaltziron of 0.2 to 2.0:1 Molar ratio of nickelziron of 0.2 to 2.0:1

and the metal ferrite being formed by heating the mixture at a temperature between about 1400 to 2000 FL for a period of about 1 to 24 hours.

2. The method of claim 1 wherein said intimate mixture is calcined at a temperature of at least 1800 F.

3. The method of claim 1 wherein the intimate mixture which is calcined contains a molar ratio of cobalt and/ or nickelziron of 0.5 :1.

4. The method of claim 1 wherein said metal ferrite is extended upon a carrier.

5. The method of claim 1 wherein said hydrocarbon oil is a petroleum naphtha.

6. The method of claim 5 wherein said naphtha is an oleinic naphtha.

7. The method of desulfurizing a petroleum naphtha which comprises contacting said naphtha at a temperature between about 600 and 1000" F. and at a pressure of about to 3000 p. s. i. g. in the presence of hydrogen with a catalyst containing as the essential component at least one metal ferrite selected from the group consisting* of cobaltous ferrite and nickelous ferrite which metal ferrite is prepared by calcining an intimate mixture of a compound affording an oxide of iron and a compound affording an oxide of a metal selected from the class consisting of cobalt and nickel, the intimate mixture containing the metals in the following ratio:

Molar ratio of cobaltziron of 0.5 :1 Molar ratio of nickelziron of 0.5 :l

Vand the metal ferrite being formed by heating the mixture at a temperature between 1800J and 2000 F. for a period of about 1 to 24 hours.

8. The method of claim 7 wherein the intimate mixture being colcined is a mixture of nickel oxide and iron oxide.

References Cited in the file of this patent UNITED STATES PATENTS 1,932,174 Gaus et al. Oct. 24, 1933 1,932,186 Pier et al. Oct. 24, 1933 1,996,008 Kaehler et al. Mar. 26, 1935 FOREIGN rlATl-ENIS 717,301 France Oct. 19, 1931 

1. THE METHOD OF DESULFURIZING A HYDROCARBON OIL CONTAINING ORGANIC SULFUR COMPOUNDS WHICH COMPRISES CONTACTING SAID OIL IN THE PRESENCE OF HYDROGEN AT A TEMPERATURE BETWEEN ABOUT 600* AND 1000*F. WITH A CATALYST CONTAINING AS THE ESSENTIAL COMPONENT AT LEAST ONE METAL FERRITE SELECTED FROM THE GROUP CONSISTING OF COBALTOUS FERRITE AND NICKELOUS FERRITE WHICH METAL FERRITE IS PREPARED BY CALCINING AN INTIMATE MIXTURE OF A COM- 